Resin-forming composition and use thereof

ABSTRACT

A composition substantially comprising diallylphthalate prepolymer and acrylonitrile or a mixture of acrylonitrile and an alkylacrylate is cured by means of an electron beam as well as other ionizing radiations to form a cross-linked resin having excellent properties. A vinyl phosphate incorporated in the composition makes the cured coating anticorrosive and adhesive to metal surface. The composition is useful as a coating or adhesion agent, or for the manufacture of decorative plywood, colored coiled steel sheet, etc., and for preparing an anticorrosive paint.

United States Patent [191 Gotoda et a1.

[451 Sept. 30, 1975 RESIN-FORMING COMPOSITION AND USE THEREOF Inventors: Masao Gotoda, Hirakata; Kenji Yokoyama, Ikeda; Yoshimi Kono, Amagasaki; Shigekazu Toyonishi, Sakai; Kunio I-Iiwano; Takaitsu Shimoyama, both of Hiroshima, all of Japan Assignee: Japan Atomic Energy Research Institute, Tokyo, Japan Filed: Mar. 27, 1973 Appl. No.: 345,333

Related US. Application Data Division of Ser. No. 240,862, March 31, 1972, Pat. No. 3,869,341, Continuation of Ser. No. 35,644, May 8, 1970, abandoned.

Foreign Application Priority Data May 9, 1969 Japan 44-35236 US. Cl. 204/l59.22; 204/l59.15;

' 260/78.5 UA Int. Cl. C08F 2/46; C08F 218/18 Field of Search ..260/78.4 UA, 78.5 UA,

78.5 E; 204/l59.15, 159.22, 159.23; 117/93,31; 156/272; 16l/412,268,270

/ [56] References Cited UNITED STATES PATENTS 2,958,673 11/1960 Yunjen 260/45.5 2,990,388 6/1961 Johnston et a1. 260/23 3,074,866 1/1963 DAlelio 204/154 3,081,244 3/1963 Campanile 204/154 FOREIGN PATENTS OR APPLICATIONS 949,191 2/1964 United Kingdom; 204/l59.15 983,234 2/1965 United Kingdom 260/78.4

Primary Examiner-Joseph L. Schofer Assistant Examiner-John Kight, Ill

Attorney, Agent, or FirmStevens, Davis, Miller & Mosher preparing an anticorrosive paint.

10 Claims, 1 Drawing Figure US. Patent 56 9901975 3,909,379

IOO- 0 0 0 O: CURVE LINE A CONVERSION OF MONOMER (WEIGHT X CURVE LINE B 2 4 6 8 IO (M rad) DOSE OF ELECTRON BEAM RESIN-FORMING COMPOSITION AND USE THEREOF CROSS-REFERENCE TO RELATED APPLICATION This is a division, of application Ser. No. 240,862, filed Mar. 31, 1972, now US. Pat. No. 3,869,341, which is in tum-a continuation of application Ser. No. 35,644, filed May 8, 1970 now abandoned.

This invention is based on the invention titled A process for curing synthetic resin composition by means of ionizing radiation filed on Jan. 19, l970, application Ser. No. 4,093 being assigned, now abandoned. Said invention relates to a process for preparing a cross-linked polymer which comprises curing a mixture of diallylphthalate prepolymer and a polymerizable vinyl monomer by means of an ionizing radiation. The present invention is a further development of said prior invention, and employs a polymerizable monomer comprising acrylonitrile or a mixture of acrylonitrile and an alkylacrylate as the vinyl monomer component and the resulting product can be advantageously used as a coating or a bonding agent or in the manufacture of decorative plywood, etc.

BACKGROUND OF THE INVENTION Radiation-curable resin-forming compositions, such as unsaturated polyesters dissolved in a vinyl monomer such as styrene, are known. However, these resin materials shrink too much upon curing and, also, they are inferior in resistance to water and chemicals and in electrical properties, because they retain residual functional groups such as hydroxyl, carboxyl at the ends of their molecular structure.

The main features of this invention and said prior invention lie in employment or selection of diallylphthalate prepolymer which eliminates the above-mentioned defects and disadvantage of the known resin-forming compositions.

The polymerization (curing) of diallylphthalate resin ordinarily requires rather drastic conditions, such as hot pressing, because of the degradative chain transfer which is intrinsic to allyl compounds. Diallylphthalate prepolymer usually has the straight chain structure comprising 30 50 units, in which concentration of the residual allyl double bond is high. However, it shrinks very little during curing, and it gives a hard polymer body having densely distributed cross-linkings which has excellent dimensional stability. Further, this material is free from the residual functional groups such hydroxyl and/or carboxyl, etc. It is not only superior to unsaturated polyester materials in resistance to water and chemicals, but also it has good weathering resistance and it is superior in electrical properties.

An unsaturated polyester material contains residual functional groups and the double bonds in its main chain are derived from maleic acid etc. In contrast, in the main chain of diallylphthalate prepolymer, there exists no functional group, and the curing reaction depends solely upon graft polymerization by cross-linking of the ,allyl double bonds remaining in the branches and the vinyl monomer. The difference in the structure of the main chain between the unsaturated polyester and diallylphthalate prepolymer accounts for the latters stabilizing the cured resin, and making it resistant to weathering. It is a cause of the excellence of the resin composition of this invention. That is, the polymer obtained by the process of this invention retains the qualities of the diallylphthalate which give it superior resistance to weathering, water and chemicals, and give it dimensional stability and excellent electrical properties.

SUMMARY OF THE INVENTION This invention relates to a composition of a crosslinked polymer material, the method for curing the composition and the use of said composition. More particularly, this invention relates to a cross-linkable polymerizable composition comprising diallylphthalate prepolymer dissolved in acrylonitrile or a mixture of acrylonitrile and an alkylacrylate, if desired together with another vinyl monomer, containing a reaction promoter such as radical initiator if desired, which is polymerized (cured) by means of an ionizing radiation, preferably by an electron beam irradiation, and relates to processes for coating, adhesion and manufacturing decorative laminate plywoods, etc., using said composition and, further, to the products thereof.

Though diallylphthalate prepolymer is easily ob-v tained, it is difficult to polymerize diallylphthalate to higher degree, since a degradative chain transfer takes place during its polymerization. The diallylphthalate prepolymer used in the invention of this application is obtained by polymerizing diallylphthalate by the conventional method, stopping the polymerization before gelling takes place and separating the unreacted monomer. The degree of polymerization of the prepolymer for use in this invention is not strictly limited, but a prepolymer having softening point in the range of 50 110C. iodine value in the range of 45 65, viscosity (as 50% methyl ethyl ketone solution) in the range of 35 llO cp (30C) is preferable.

Also, the proportion in mixing diallylphthalate prepolymer and the vinyl monomer is not restricted. However, hardening is retarded as the concentration of vinyl monomer increases, and therefore, the proportion of vinyl monomer is most suitable for use in the range of 30 by weight of the mixture.

The resin-forming composition of this invention can be cured by various ionizing radiations, but one feature of this invention is thatthe composition is curable by a radiation of high dose rate (e.g., an electron beam from a high power accelerator) and, therefore, curing is effected in an extremely short period of time. This is a great advantage in industry, especially in such fields as the manufacture of plywood and the continuous coating of coiled steel sheets. Incidentally, radical catalysts (free radical initiators) such as benzoyl peroxide can be added to the resin-forming mixture to reduce the radiation dose and increase the degree of curing.

The curing is satisfactorily effected when irradiation is carried out in air, but the radiation dose can be reduced further if the irradiation is carried out in an inert gas such as nitrogen or in an atmosphere maintained at low oxygen concentration.

When a small amount of a phosphate having a reactive vinyl group or groups is added to the above resinforming composition, the adhesion and anticorrosive properties of the cured coating thereof are remarkably improved.

Some of the preferred modes of practice of this invention are summarized below:

A. According to one embodiment of this invention, a resin-forming composition comprising diallylphthalate prepolymer, acrylonitrile and an alkylacrylate is provided. This composition provides a decorative coating that has excellent resistance to chemicals and solvents, resistance to heat, adequate hardness, and beautiful lustre. As a coating for metallic materials, it has excellent adhesion and suitable flexibility. Further, it can be used in the manufacture of wood-polymer composites (WPC).

This composition is cured by means of an ionizing radiation, and if desired, a radical catalyst such as benzoyl peroxide can be incorporated in the composition. Because it employs acrylonitrile, the cost of this composition is relatively low. The composition is curable by means of an ionizing radiation, and high speed continuous curing processing is possible by employing an electron accelerator with low voltage and high current intensity. The excellent resistance to solvents character istic of diallylphthalate prepolymer and polyacrylonitrile is retained in. the cured resin obtained from this composition by irradiation, and further the dimensional stability and resistance against weathering characteris tic of diallylphthalate resin are retained and its electrical properties are excellent, too.

The thus formed resin is superior as a coating for metal surfaces. Most conventional coating materials are a solution or emulsion of vehicle and pigment, and the coating is formed simply by evaporating the solvent or dispersion medium. Some materials are comprised of two liquid components, which harden when united. In the composition in accordance with this invention, the reactive monomers used as the solvent participate in the curing reaction; they contribute to formation of the coating film and their conversion is about 100%.

In the prior art, it was known that modifying alkyd resin with acrylonitrile improved resistance of the resin to oil and solvents. However, if too much acrylonitrile is used, the product gells and no resin is obtained, so reportedly, no more than 6% of acrylonitrile can be used in the modification. In contrast, in this invention, acrylonitrile is used in combination with diallylphthalate prepolymer as the solvent for the latter before the stage of polymerization, and therefore enough acrylonitrile to dissolve the prepolymer can be used without causing gelling and the properties characterisitc of polyacryl onitrile are fully exhibited in the obtained resin.

Because of its excellent adhesive nature, this resinforming composition can advantageously be used for coating metal surfaces. But the resin derived from the diallylphthalate prepolymer acrylonitrile system lacks flexibility and therefore it is not suitable for a coating in which flexibility is required, such as coating for coiled steel sheets. We have found that a flexible coating with the same adhesion power is obtained by adding to this resin-forming system a polymerizable monomer, such as alkylacrylate, that forms a polymer which has a low second order transition point. The thus obtained metal coating is provided with excellent resistance to chemicals, oils and weathering and also has the selffire-extinguishing nature inherent to diallylphthalate resin.

Further the resin-forming composition of this embodiment can be very advantageously applied to manufacturing woodpolymer composite, the so-called WPC. Among the methods for manufacturing WPC known so far is the impregnating of wood with a reactive monomer such as methyl methacrylate, then polymerizing said monomer by heating or gamma radiation (that is from a Co-6O source). However, this method is not so efficient, and the resin formed is thermoplastic and therefore is inferior in resistance to heat, chemicals and solvents. In contrast, the resin-forming composition of this invention can be cured in the tissue of wood not only by gamma radiation but also by electron beam, and therefore WPC can be manufactured in a short period of time and continuously within the penetration range of an electron beam. As the thus obtained resin is three-dimensionally cross-linked, the manufactured WPC has excellent dimensional stability as well as resistance to water, chemicals, solvents and weathering.

The proportions of components for the resin-forming compositions in accordance with this embodiments of the invention are as follows:

wherein DAP stands for diallylphthalate prepolymer, AN for acrylonitrile, AA for alkylacrylate and BPO for benzoyl peroxide. The numbers denote weight ratio. Alkylacrylate, the alkyl group of which has 1 5 carbon atoms, can easily be used. When a relatively hard coating is desired, an acrylate having a lower alkyl group such as methyl or ethyl is preferred, and when flexibility is required, an acrylate having higher alkyl group containing more than 3 carbon atoms is preferred.

In curing the resin-forming composition in accordance with this embodiment, it is effective to carry out polymerization in an oxygen-free environment, e.g., in a nitrogen stream or while the surface of the coated composition is covered by a film or sheet. Also, if a radical catalyst, such as benzoyl peroxide is added to the composition, the radiation dose can be reduced.

B. According to another embodiment of this invention, a novel plywood material and a novel method for manufacturing the same is provided. The novel plywood comprises a thin wooden surface layer (veneer) comprising wood polymer composite (WPC) and a substrate component, and the finished product is useful as a material for floor, wall, cabinets, etc. The method of manufacturing it is characterized by carrying out preparing the WPC surface component and bonding it to the substrate component simultaneously; further, if desired, surface coating of the WPC surface component can also be carried out simultaneously.

The higherto known composite wood materials such as floor board are manufactured by applying a l 3 mm thick veneer of a high class hard wood such as oak, zelkova, etc. to a substrate by means of a suitable adhesive, and coating the surface of the veneer with urethane or amino alkyd resin coating materials. Such a composite wood board is expensive because it requires complicated manufacturing steps and uses high class hard wood materials; still, its surface coating is not so durable. In contrast, in this invention a thin layer of low In the prior art, WPC is manufactured mainly by impregnating wood material with a vinyl monomer such as methyl methacrylate or styrene and polymerizing said monomer either by heating or by irradiation. However, the resin formed according to such a prior art method is thermoplastic and therefore it can not be surface-polished with a sander and moreover, it is impossible to carry out high speed curing with an electron beam using a higher dose rate.

The WPC which is manufactured in accordance with this embodiment of the invention comprises a cured resin which has been three dimensionally cross-linked, and thus it can be polished with a sander and also has dimensional stability, improved abrasion resistance and resistance to moisture, oils and solvents.

The resin-forming composition suitable for this embodiment of the invention comprises a vinyl monomer solution of diallylphthalate prepolymer, but another reactive prepolymer such as unsaturated polyester can advantageously be added. As to the vinyl monomer, in view of its solvent power for prepolymers and the physical properties of the obtained resin, acrylonitrile is preferable, but, if necessary, other monomers can be used in addition to acrylonitrile which is the main solvent monomer. In order to accelerate thecuring reaction, a radical catalyst such as benzoyl peroxide can be advantageously be added in an amount not more than 4%, preferably 0.5 1% by weight whole composition. Though there is not strict limitation on the mixing ratio of the prepolymer and the monomer, in the light of the reaction velocity and ease of impregnation, the preferred ratio is around 50 50.

Impregnation can easily be performed by the conventional methods (vacuum impregnation, pressure impregnation or a combination thereof). The curing of the resin composition can be carried out by means of any of ionizing radiation such as gamma radiation, X- rays and electron beam, however, use of an electron beam is advantageous since it makes continuous manufacturing possible. Needless to say, the electron beam must be strong enough to penetrate the veneer and the resin layer thereunder. This is the most important feature of this invention. It is the penetration of both veneer and resin layer that makes it possible to manufacture a novel plywood material suitable for floor, wall, siding cabinets, etc., in one step. That is, in this invention, a veneer impregnated with the above-mentioned resin-forming composition is pressed against the surface of a substrate board and the thus formed composite is passed, while under slight pressure, through the electron beam, whereby the resin-forming composition acts as the adhesive, too. Further, if it is desired to coat the surface of the veneer, this is easily achieved in the same step by applying a suitable mold-release film or sheet e.g. of Mylar (RTM) on the resin-forming composition remaining on the surface of the veneer upon impregnation, stretching said sheet well to expel bubbles, then passing the composite through electron beam. In this case, there is, of course, no need for a polishing step. Various surface effects are achieved by controlling the amount of the resin-forming composition remaining on the surface of the veneer, or by using pattern-embossed mold release sheets.

An electron beam dose of 2 to Mrad is required for curing the composition, and the preferred dose is about 4 to 8 Mrad. A dose of 6 Mrad will effect more than 90% and a dose of 8 Mrad about 100% conversion of monomer. In this embodiment, a Van de Graaf electron accelerator is used at 1.5 MeV and lOOuA. In case gamma rays from Co-60 at the dose rate of 0.1 Mrad/- hour are employed, more than conversion of monomer is achieved with a dose of 0.1 Mrad and about with a dose of 0.2 Mrad.

C. According to still another embodiment of this invention, a novel composition which is an improvement of the embodiment (A) is provided as an excellent coating materials. This embodiment is characterized in that a phosphate having a reactive vinyl group or groups (hereinafter referred to as a reactive vinyl phosphate) is added to the composition of this invention, in order to improve adhesive properties and incorporate excellent anticorrosive properties without any adverse effect on the curing of the composition.

The reactive vinyl phosphates incorporated in this composition form a copolymer by reacting mainly with a vinyl monomer and with diallylphthalate prepolymer. This composition improves the bonding and anticorrosive properties when coated for example on an iron surface, presumably owing to formation of complex bonds between the phosphoric acid residue and the iron surface. Furthermore, according to this embodiment, a stable coating the bonding property of which is kept unchanged for long time isobtained, since the vinyl phosphate added to the composition reacts with the coating vehicle by way of copolymerization. The reactive vinyl phosphate is of the type in which the vinyl group of the phosphate either bonds directly with phosphor atom or indirectly with it holding oxygen atom etc. between them. As the type of ester of phosphoric acid, monoester or diester is usually employed and triester can also be used. The vinyl phosphates which are employed in this embodiment typically include a phosphate of a hydroxyalkyl-methacrylate, a phosphate of a hydroxyalkylacrylate, a vinyl phosphonate, etc.

The paint prepared according to this embodiment is provided with sufficient anticorrosive property by adding an ordinary inert pigment, whereas most of the conventional anticorrosive paints contain the basic anticorrosive pigments such as zinc chromate and basic lead chromate etc. The above-mentioned characteristic is due to the excellent electrical resistance of a paint vehicle containing diallylphthalate prepolymer as well as the effect of a vinyl phosphate additive.

The coating composition of this invention comprises a resinous solution in which about 30 to 70 parts (preferably 40 to 60 parts) of diallylphthalate prepolymer are dissolved in about 70 to 30 parts (preferably 60 to 40 parts) of a mixture substantially consisting of acrylonitrile and at least one alkylacrylate, together with a reactive vinyl phosphate (generally 0.005 0.05 mol per 100g of the monomer mixture), if desired being incorporated with a radical polymerization catalyst. If desired, a pigment can be formulated by milling with the coating composition.

As disclosed in the explanation of the embodiment (A), the increase in acrylonitrile component enhances hardness and solvent resistance of the cured coatings, and as the carbon number of alkyl group of alkyl acrylate increases, the cured coating becomes flexible. The coating composition is further characterized in that it can be cured in an extremely short period of the second unit by means of an electron beam of high dose rate from a low voltage and high amperage accelerator.

The composition of this embodiment was coated on polished mild steel plates and cured by means of an ionizing radiation under nitrogen flow. It was then tested by cross-cut adhesion test, Erichsen test, impact test,

immersion test in aqueous sodium chloride solution and immersion test in toluene or xylene etc. These tests prove that the cured coatings obtained after applying the coating composition are suitable as an anticorrosive primer for ships. A coating material employed as a primer must serve as a suitable base for a topcoat. The cured coatings prepared as above were top-coated with oil, chlorinated rubber, vinyl resin, epoxy resin and tarepoxy resin series paints respectively. The abovementioned tests were carried out on these top-coated samples, and no defect such as peeling between the coated layers was found.

One of the characteristics of this invention is that no solvent is required in this coating composition. However, when it is necessary to decrease the viscosity of the composition for particular applications, a highly volatile low-boiling organic solvent such as acetone etc., which evaporates rapidly and does not prevent polymerization reaction, can be added to this coating composition. The use of such solvent has substantially no adverse effect on the curing of the coated composition.

BRIEF DESCRIPTION OF THE DRAWING The attached drawing illustrates the conversions of monomers when some of the resin-forming compositions of the present invention are cured.

DESCRIPTION OF THE PREFERRED EMBODIMENTS:

Now the invention is illustrated by way of working examples. In these examples, the amount of the components is shown by weight.

EXAMPLE 1 A resin-forming composition was obtained by dissolving l parts by weight of diallylphthalate prepolymer (iodine value 56, softening point 80 95C, the same prepolymer being employed in Examples 1 6) and 4 parts by weight of commercially available benzoyl peroxide in a mixture of 60 parts by weight of commercially available acrylonitrile and 20 parts by weight of commercially available methacrylate to give a homogeneous mixture. This composition was poured on the surface of a plywood board laminated with printed paper at the rate of l80g/m The coated surface was covered with a mold release sheet, which was pressed and stretched well to expel bubbles. The composite was subjected to electron beam irradiation of 6 Mrad from a Van de Graaff electron accelerator 1.5 Mev. lOOuA, 0.5 Mrad/sec). A stable and durable decorative surface coating with beautiful lustre was obtained. The obtained product passed all the tests carried out in accordance with JAS and JIS. The tests include Test for Resistance to Chemicals (passed tests with acetic acid, 1% sodium carbonate solution, methanol, toluene, acetone, carbon tetrachloride, chloroform); Repeated Heating and Cooling Test (A cycle of heating at 100C for 2 hours and cooling at -20C for 2 hours was repeated five times, and no change was observed); Soiling Test (passed test with mercurochrome and black shoe polish, slightly stained with iodine tincture); Test against Cigarette (passed); Test for Machinability with Electric Saw (passed).

EXAMPLE 2 A resin-forming composition was prepared by dissolving l00 parts by weight of diallylphthalate prepolymer (the same as that of Example 1 and 3 parts of benzoyl peroxide in 100 parts by weight of acrylonitrile to give a homogeneous mixture. Example 1 was repeated using this composition. A durable and beautiful decorative coating with lustre was obtained by electron beam irradiation of 5 Mrad.

EXAMPLE 3 A resin-forming composition was prepared by dissolving 100 parts by weight of diallylphthalate prepolymer (the same as that of Example 1 and 4 parts by weight of benzoyl peroxide in a mixture of 90 parts by weight of commercially available butylacrylate and 10 parts by weight of acrylonitrile to give a homogeneous mixture. This composition was applied on a surface of a steel plate (JIS G 3310, 0.5 X 50 X 150 mm) which had been degreased with toluene and polished with sand paper (No. 120), and the coated surface of about 30 in thickness was covered by the mold release sheet which was stretched to expel bubbles as in Example 1. By electron beam irradiation of 5 Mrad a clear coating with lustre was obtained on the metal surface. The coated steel plate was subjected to the following tests at 20C and humidity.

Bending test: The plate was bent at an angle of 180 around an axis of 2 mm in diameter with the coated surface outside. The coating was not damaged.

Drawing test: A circle 10 mm in diameter was drawn with a total load of 400g, the coating did not suffer any peel-off.

Cross-cut Adhesion Test: 100/100 Impact Test: The results of the test by means of the Impact Test by Dupont type method; (Load: 1 Kg. Fall: 50 cm, Diameter of hammer: one-half inch) no observable damage to the coating.

EXAMPLE 4 A resin-forming composition was prepared by dissolving 100 parts by weight of diallylphthalate prepolymer (the same as that in Example 1) and 4 parts by weight of benzoyl peroxide in a mixture of parts by weight of commercially available ethylacrylate and 10 parts by weight of acrylonitrile to give a homogeneous mixture. This composition was applied on the surface of a steel plate and given electron beam irradiation of 4 Mrad in accordance with the operation of Example 3. A clear coating with lustre was formed on the metal surface.

EXAMPLE 5 A resin-forming composition was prepared by dissolving parts by weight of diallylphthalate prepolymer (the same as that in Example 1) and 0.5 part by weight of benzoyl peroxide in a mixture of 90 parts by weight of acrylonitrile and 100 parts by weight of methylacrylate to give a homogeneous mixture. A piece of beech wood 80 X 30 X 8 mm in dimension was impregnated with the composition in vacuo for 4 hours (84% impregnation). The piece was covered with aluminium foil and was subjected to electron beam irradiation of 4 Mrad. Conversion of monomers was 93%. When it was subjected to irradiation of 6 Mrad, conversion was 98%, which is almost complete curing.

On the other hand, the composition comprising 100 parts by weight of diallylphthalate prepolymer, 0.5 parts by weight of benzoyl peroxide was dissolved in 100 parts by weight of acrylonitrile achieved only 88% conversion when impregnation of wood was effected as above (85% impregnation) and was given electron beam irradiation of 4 Mrad.

curing, a beautiful surface of wood-polymer composite was obtained by polishing the cured resin surface.

EXAMPLE 9 Five 1 X 30 X 30 mm pieces of birch-tree board were impregnated with the resin-forming composition in the same way as Example 7, covered with aluminium foil and irradiated with electron beams of 2, 4, 6, 8 and 10 Mrad respectively. The unreacted monomers were 10 evaporated by keeping the cured samples at the tem- EXAMPLE 6 perature of 50C and at the reduced pressure of l A resimforming composition was prepared by mmHg for 2 days. Curve line A of the attached drawing solving 50 parts by weight of diallylphthalate pre shows conversions of the monomers which were calcumer (the same as that in Example 1) in a mixture of 45 lated from the Welght changes of the samplesparts by weight of acrylonitrile and 5 parts by weight of EXAMPLE 1O methylacrylate to give a homogeneous mixture. The composition was coated on the surface of a steel plate Fwe l X 30 30 mm plices of Puch'tree Pf were and given electron beam irradiation of 4 Mrad in accor- {P w1t h the resm'forfmng composltlon dance with the operation of Example 3. The conversion SStmg of 50 Weflght parts of dlallyllihtbalte prepoly' of monomers was 67.2%. When the composition premet 50 weght parts acrylomtnle the Same pared by adding 4 parts by weight of benzoyl peroxide W a m Efample The impregnated Samples were to the above resin-forming composition was employed, lrradlated electron beams of 8 and 10 a remarkably higher conversion of 915% was Mrad respectively. The unreacted monomers were achieved evaporated by keeping the cured samples at 50C and under the pressure of l mrnHg for 2 days. Curve line EXAMPLE 7 B shows conversions of the monomers.

A l X 50 X 50 mm piece of birch-tree board was de- E M E 1 1 gassed by placing it in a dessicator at the reduced pressure of 1 mmHg for one hour, and was impregnated A 3 X 30 l plea? of beech P l l with the resin-forming composition consisting of 50 30 nated .wlth the reslmformmg Composmon conslstmg of weight parts of diallylphthalate prepolymer, 50 weight j gz F of iz q i i prepogmear 2 3 2 parts of acrylonitrile and 1 weight part of benzoyl per- 3 5;: g g z g s g t oxide, by dipping it in the composition for 3 hours. The E a i. 8 Mrad d p birch-tree board impregnated with the composition was 6 m rra la 10 an e O 0 mg .laminated with a 5 X cm veneer board 4mm thicktable compares dimensional changes in the sample and The laminated sample was covered with a Mylar moldan lmtreated beech.board' The test was earned f by release sheet and bubbles were removed by stretching drying the two speclmens at a temperature of 50 C and f the sheet; then the sample was given 6 Mrad of electron a.reduced prssure 1 g 5 and then beam irradiation An electron beam at the dose rate of p acmg sfpeclmens m a t ermo ygrostat ept at rel- 5 Mrad/Sec a lied ilsin a Van de Graaff also 40 ative humidity of 90% and at 40C for one month. The I pp g dimensions of a completely dry board in vacuum were acce crater d ff 1 ff h used as a standard and dimensional differences with rewhen force was apphe m an e on pee t e spect to the standard were measured. The excellent reg ii g g g z X; ifg sults confirm the high dimensional stability achieved by oar ra er an in e on e sur ace. eau l u use of the resent invention. and durable surface with lustre was obtained after rep moving the mold-release sheet. The resulting surface Table 1 was not affected at all by the solventproof test which Untreated Treated comprises contacting for 15 minutes at room temperature absorbent cottons impregnated with water, ethyl Ratio of resin impregnatemqg) 0 108 alcohol, acetone, chloroform, ethyl acetate, etc., re- Increase in weight(%) 17.7 5.2

1 Increase in dimensions spec We Tangential direction 6.1 2.0 Radial direction 2.7 L3 EXAMPLE 8 Axial direction 0.9 0.2

A 1 X 50 X 50 mm piece of birch-tree board was impregnated with the resin-forming composition in the EXAMPLE 12 Same y as Example The p g f p w Example 11 was repeated using electron beam irradi- Placed on a Substrate and the Composltlon remalflmg ation of 4 and 6 Mrad respectively. The dimensional on the surface was wiped off. Then the sample was irrachanges were measured in the Same way as Example diated with 6 Mrad of electron beam and cured. After 11 Table 2 Sample irradiated Sample irradiated with 4 Mrad dose with 6 Mrad dose Ratio of resin impregnated 75.6 102.6 Increase in weight 7.4 5.5 Increase in dimensions Tangential direction 3.0 2.4 Radial direction 2.1 1.6 Axial direction 0.2 0.2

EXAMPLE 13 Hardness test and abrasion test were carried out on the plywoods obtained by the present invention. The results are shown in'Table 3. The abrasion test was done according to the method of testing thermosetting plastics decorative laminate plywood of HS (Japanese Industrial Standards) K-6902; however, the depth of abrasion per 300 rotations was used as the basis for evaluation, since the method used for decorative laminate plywood can not be applied to these plywoods. The samples were prepared by impregnating l X 120 X 120 mm birch boards with the resin-forming solution consisting of 50 weight parts of diallylphthalate prepolymer, 50 weight parts of acrylonitrile and 1 weight part of benzoyl peroxide at the impregnation of about 100%, laminating the boards with substrates and irradiating the laminated materials with 6 Mrad of electron beam.

Table 3 being immersed for days in a 3% aqueous NaCl solution at 20C.

Xylene Immersion Test:

After being immersed in xylene for 5 days at 20C, neither blistering nor peeling occurred, although a trace of swelling was exhibited.

EXAMPLE 15 EXAMPLE 16 A coating composition was prepared by dissolving 50 Plywood with WPC Birch Board untreated EXAMPLE 14 A coating compound was prepared by dissolving 50 parts of diallylphthalate prepolymer (iodine value 56, softening point 90 95C; hereinafter the same prepolymer is employed), 40 parts of n-butylacrylate, 10 parts of acrylonitrile and 3 parts of phosphate of 2 -hydroxy-ethyl-methacrylate (monoester about 80%, diester about 20%, hereinafter the same phosphate is used except for Example 20), formulating 15 parts of black iron oxide pigment by means of a ball mill for 24 hours, and adding 2 parts of benzoyl peroxide. I

A coating thick was applied to the surface of 70 X 150 X 0.8 mm mild steel plates (JIS-G-33 10) with a bar coater. The thus coated plates were given 6 Mrad of electron beam irradiation under nitrogen atmosphere from a Van de graaff type accelerator (1.5 MV and 100p. A). Excellent results were obtained in the various tests made on the cured coatings as shown below.

Cross-Cut Adhesion Test The cured coating was cross-cut into 100 pieces of 1 mm squares by the steel needle for gramophone. A cellophane tape was put thereon, and then pulled off at an angle of 45 against the coating surface. None of the coating peeled off.

Impact Test Neither peeling nor cracking was exhibited under the Du Pont type testing (load 1 Kg, diameter of hammer one-half inch, 50 cm fall).

Immersion Test in aqueous NaCl solution:

Formation of rusts and blisters was exhibited after surface coated with the cured resin parts of diallylphthalate prepolymer, 40 parts of ethylacrylate, 10 parts of acrylonitrile and 5 parts of phosphate of 2-hydroxyethyl methacrylate, formulating 20 parts of red iron oxide pigment by means of a ball mill for 24 hours, and adding 2 parts of benzoyl peroxide. Example 14 was repeated by using thus prepared composition. The cured coating was substantially equal to that of Example 14.

EXAMPLE 17 A coating composition was prepared by dissolving 50 parts of diallylphthalate prepolymer, 40 parts of nbutylacrylate, 10 parts of acrylonitrile and 5 parts of phosphate of 2-hydroxyethyl methacrylate, formulating 15 parts of titanium dioxide pigment by means of a ball mill for 24 hours, and adding 2 parts of benzoyl peroxide. Example 14 was repeated by using thus prepared composition. The tests showed that the cured coating was by no means inferior to that of Example 14.

EXAMPLE 1 8 A clear transparent coating composition was prepared by dissolving 50 parts of diallylphthalate prepolymer in a mixture of 40 parts of n-butyl acrylate, 10 parts of acrylonitrile, 3 parts of phosphate of 2-hydroxyethylmethacrylate and 2 parts of benzoyl peroxide.

The composition was coated with a bar coater on polished mild steel plates in the same way as Example 14, followed by electron beam irradiation of 6 Mrad in the air. The same tests were carried out on the cured samples, which were found to have excellent properties.

EXAMPLE 19 The same composition as prepared in Example 18 was coated with a bar coater on polished mild steel plates, followed by electron beam irradiation of 6 Mrad in the air. The cured samples were left for one day at a room temperature, then uniformly overcoated with a polyvinyl chloride anticorrosive paint with a paint brush, and dried for one day at room temperature.

The cross-cut adhesion test and impact test were carried out on the top-coated samples in the same way as Example 14. No coating was removed by the cross-cut adhesion test. The impact test caused no peeling between the coated layers and no cracking.

EXAMPLE 20 A coating composition was prepared by dissolving 50 parts of diallylphthalate prepolymer, 40 parts of nbutylacrylate, parts of acrylonitrile and 2 parts of vinylphosphate formulating parts of black iron oxide pigment by means of a ball mill for 24 hours, and adding 2 parts of benzoyl peroxide. The composition was coated, cured and tested in the same way as in Example 14. The tests showed that the cured coating is by no means inferior to that of Example 14.

Control (Reference Example) Example 14 was repeated except that no phosphate of 2-hydroxyethyl methacrylate was added to the composition. The cross-cut adhesion test showed the residue ratio of 50 per 100 cross-cuts. The cured coating exhibited blistering andformation of rust in the immersion test with aqueous NaCl solution, and some peeling of the coating in the xylene immersion test.

What is claimed is:

1. A cured adhesive and anticorrosion coating on a substrate, said coating comprising an ionizing radiation cured composition initially comprising a solution of about -70 parts by weight of diallyl phthalate prepolymer in a mixture consisting essentially of acrylonitrile and at least one alkyl acrylate.

2. A cured adhesive and anticorrosion coating on a substrate, said coating comprising an ionizing radiation cured composition initially comprising a solution of about 30-70 parts by weight of diallyl phthalate prepolymer in a mixture consisting essentially of acrylonitrile, at least one alkyl acrylate, and a reactive vinyl phosphate.

3. The cured coating of claim 2 wherein said reactive vinyl phosphate is selected from the group consisting of: phosphates of hydroxyalkyl-methacrylates and phosphates of hydroxyalkylacrylates.

4. A cured paint coating comprising the cured coating of claim 2, wherein said initial composition additionally comprises a suitable amount of a pigment.

5. The cured coating of claim 4 wherein the reactive vinyl phosphate is present in an amount in the range of about 0.005-0.05 moles per g. of the prepolymer mixture.

6. The cured coating of claim 2 wherein the reactive vinyl phosphate is present in an amount in the range of about 0.005-0.05 moles per 100g. of the prepolymer mixture.

7. The cured coating of claim 1 wherein the alkyl groups of said alkyl acrylates comprise one to five carbon atoms.

8. The cured coating of claim 2, wherein the alkyl groups of said alkyl acrylates comprise one to five carbon atoms.

9. A process for preparing a crosslinked adhesive and/or anticorrosive cured coating which comprises curing by means of an ionizing radiation a solution of about 30-70 parts by weight of diallyl phthalate prepolymer in a mixture consisting essentially of acrylonitrile and at least one alkyl acrylate, said solution being curable with an electron beam dosage of about 2-10 Mrad.

10. A process for preparing a crosslinked adhesive and/or anticorrosive cured coating which comprises curing by means of an ionizing radiation a solution of about 30-70 parts by weight of diallyl phthalate prepolymer in a mixture consisting essentially of acrylonitrile and at least one alkyl acrylate, said solution being curable with a gamma ray dosage of greater than about 0.1 Mrad. 

1. A CURED ADHESIVE AND ANTICORROSION COATING ON A SUBSTRATE, SAID COATING COMPRISING AN IONIZING RADIATION CURED COMPOSITION INTIALLY COMPRISING A SOLUTION OF ABOUT 30-70 PARTS BY WEIGHT OF DIALLYL PHTHALATE PREPOLYMER IN A MIXTURE CONSISTING ESSENTIALLY OF ACRYLONITRILE AND AT LEAST ONE ALKYL ACRYLATE.
 2. A cured adhesive and anticorrosion coating on a substrate, said coating comprising an ionizing radiation cured composition initially comprising a solution of about 30-70 parts by weight of diallyl phthalate prepolymer in a mixture consisting essentially of acrylonitrile, at least one alkyl acrylate, and a reactive vinyl phosphate.
 3. The cured coating of claim 2 wherein said reactive vinyl phosphate is selected from the group consisting of: phosphates of hydroxyalkyl-methacrylates and phosphates of hydroxyalkylacrylates.
 4. A cured paint coating comprising the cured coating of claim 2, wherein said initial composition additionally comprises a suitable amount of a pigment.
 5. The cured coating of claim 4 wherein the reactive vinyl phosphate is present in an amount in the range of about 0.005-0.05 moles per 100 g. of the prepolymer mixture.
 6. The cured coating of claim 2 wherein the reactive vinyl phosphate is present in an amount in the range of about 0.005-0.05 moles per 100g. of the prepolymer mixture.
 7. The cured coating of claim 1 wherein the alkyl groups of said alkyl acrylates comprise one to five carbon atoms.
 8. The cured coating of claim 2, wherein the alkyl groups of said alkyl acrylates comprise one to five carbon atoms.
 9. A process for preparing a crosslinked adhesive and/or anticorrosive cured coating which comprises curing by means of an ionizing radiation a solution of about 30-70 parts by weight of diallyl phthalate prepolymer in a mixture consisting essentially of acrylonitrile and at least one alkyl acrylate, said solution being curable with an electron beam dosage of about 2-10 Mrad.
 10. A process for preparing a crosslinked adhesive and/or anticorrosive cured coating which comprises curing by means of an ionizing radiation a solution of about 30-70 parts by weight of diallyl phthalate prepolymer in a mixture consisting essentially of acrylonitrile and at least one alkyl acrylate, said solution being curable with a gamma ray dosage of greater than about 0.1 Mrad. 